Metal salts of organic acids of phosphorus



METAL SALTS OF ORGANIC ACIDS F PHQSPHGRUS Alexander H. Popln'n, Newark,N. J., assignor to Esso Research and Engineering Company, a corporationof Delaware No Drawing. Application September 20, 1954, Serial No.457,298

16 Claims. (Cl. 25232.7)

This invention relates -to a novel method for preparing metal salts ofacidic phosphorus-containing organic compounds and is especiallyconcerned with the preparation of salts of weakly basic metals withacidic phosphorusand sulfur-containing organic compounds such as forexample the zinc, tin, cobalt and nickel salts of phosphosulfurizedhydrocarbons. The invention also relates to the metal salts themselveswhich are useful in lubricating oil compositions, insecticides,fungicides and the like, and to such compositions containing the metalsalts.

The utilization of metallo-organic additives in lubricating oilcompositions for internal combustion engines is well known. The additionof these materials to lubricating oils enhances their performance andproduces lubricating oil compositions having among other desirableproperties lower combustion chamber deposit-forming tendencies. Recentlyit has been found that the nature of the lubricating oil compositionsemployed and the additives incorporated therein has a substantial effecton the octane requirement of motor gasoline engines. More specifically,it has been found that after a new automobile has been driven forseveral thousand miles, the octane requirement of the car has increased.After a time, the octane re quirement of the automobile reaches anequilibrium value, and it has been determined that the nature of boththe gasoline and the lubricating oil employed contributes to this octanerequirement increase of the automobile. Because of the severity ofpresent-day engine operation and because of the criticality of octanerequirement for automobiles, there -is a need for improved lubricatingoil compositions and for improved additives for these compositions.

One particular type of lubricating oil additive which has beenextensively employed is a metal salt of a phosphosulfurized organicmaterial. Such additives have been utilized as detergents in lubricatingoil compositions to prevent the formation of engine crankcase depositsand thus to improve the operation of the engines. These additives havebeen prepared in the past by treating a phosphosulfurized organicmaterial at an elevated temperature with a basic reagent containing ametal constituent such as a metal oxide, 2. metal hydroxide, or a metalcarbonate. Although this method has been employed to producephosphorus-containing metallo-organic compounds of potassium and barium,for example, this particular method has not been effective for producinggood yields of the compounds of weakly basic metals such as zinc, tin,nickel, cobalt, etc. There has thus been a need for an effective processfor producing such salts since these phosphorusand sulfur-containingsalts are exceedingly effective as detergent additives and in additionhave various other uses in such fields as insecticides, fungicides andthe like. Heretofore it is not believed that there was such a method.

A novel method has now been found for preparing phosphorus-containingmetallo-organic compounds of weakly basic metals, such as zinc, tin,cobalt, nickel and the like. Briefly, the method of the presentinvention comprises reacting an acidic phosphorus-containing or- StatesPatent "ice 2 ganic compound with an aqueous acidic solution of a metalhalide at an elevated temperature for a period of time suflicient toproduce a substantially dry metal salt of the acidicphosphorus-containing organic compound. The metal which may be used inthis method is one having an electrode potential in the electromotiveseries in the range of about 0 to 2.0 volts. A suflicient amount of themetal halide is employed in the reaction to form a salt of thephosphorus-containing organic compound. The method of this invention isunique and unexpected, involving the replacement in a salt of a strongacid by a Weak acid. More particularly, the halogen atoms of the metalhalide are replaced by the acidic phosphorus-containing organiccompound. The reaction is carried out at an elevated temperature,preferably in the range of about 140 to 300 F., until most of the waterhas been driven off from the reaction mixture, after which thetemperature may be raised to as high as about 500 F. to assuresubstantial completion of the reaction. It has been found that themethod of this invention may be best carried out by employing an aqueoussolution of the metal halide and a small amount of preferably a halogenacid which is believed to act as a catalyst in the reaction. Themetallo-organic compounds so formed may be employed as additives inlubricating oil compositions in concentrations of about 0.5 to 12% Theacidic phosphorus-containing organic materials of this invention may ingeneral be prepared by treating an organic material with a sulfide oroxide of phosphorus by procedures Well known to the art. Sulfides ofphosphorus such as P253, P255, P483, P487, and preferably phosphoruspentasulfide, P255, may be employed. It will be understood of coursethat mixtures of elemental sulfur and phosphorus may also be utilizedfor this purpose. When the organic material is treated with an oxide ofphosphorus, P203, P205, P403, P407 and preferably phosphorus pentoxide,P205, may be employed. The phosphorization or phospho-sulfurizationreaction is generally carried out at a temperature of about 200 to about600 F and preferably from about 300 to about 550 F., using from about 1to about 10, and preferably about 2 to about 5, molecular proportions ofthe organic material to 1 molecular proportion of the oxide or sulfideof phosphorus. It is usually desirable to use an amount of the oxide orsulfide of phosphorus which will react substantially completely with theorganic material such that further purification of the product isunnecessary. The reaction time is generally not critical, the timerequired being that necessary for substantial completion of thereaction, that is to cause substantially a maximum amount of the sulfideor oxide used to react under the temperature conditions employed. Areaction time from 2 to 10 hours in the preferred temperature range of300 to 550 F. is generally necessary. Catalysts such as organic orinorganic peroxides may be employed in the reaction. If desired, thereaction product may be further treated by blowing with steam, alcohol,ammonia, or the like, at an elevated temperature in the range of about200 to about 600 F. to improve the odor thereof.

A wide variety of organic materials may be reacted with the oxides orsulfides of phosphorus. Especially preferred organic materials arehydrocarbon polymers, oxygen-containing hydrocarbon polymers and complexorganic esters and ethers. More specifically, monoolefin polymers havingmolecular weight ranges from about to 50,000 and obtained by thepolymerization of low molecular weight olefins such as ethylene,propylene, isobutylene, amylene and the like, may be employed. Thepolymerization reaction is carried out by methods well known to the art.

Oxygen-containing hydrocarbon polymers, having molecular weight rangesfrom about 100 to 50,000 and such ratio of carbon-hydrogen to oxygen asto be oil-soluble, which are obtained by the polymerization ofoxygencontaining olefins such as vinyl ethers, vinyl esters, ma'leateand fumarate esters, and copolymers" of such materials may also beemployed. Specific oxygen-containing compounds of this type include thepolymers or copolymers of the following:

Vinyl acetate Lorol B furnarate 1 Lorol B maleate 1 Tridecyl itaconateVinyl l'auryl ether Butoxyethyl vinyl ether fDeriyed from Lo -01 3alcohol which is a commercially available saturated straight chainmonohydric alcohol product having an average of about 13.5 carbon atomsper molecule, made by hydrogenation of coconut oil.

As examples of the complex esters and others which may be treated withan oxide or sulfide of phosphorus, the following may be mentioned:

Polyalkylene oxide mono alkyl ethers Polyalkylene oxide dialkyl ethersPolyalkylene oxide mono ester mono ethers' Diesters of polyalkyleneoxide Complex forma'ls Specific complex esters and 'ethers include thefollowing:

Polypropylene oxide mono butyl ether Polyethylene oxide methyl butylether Polypropylene oxide isodecyl ether acetate Dioctanoic ester ofpolypropylene oxide Bis tridecoxy tetradecaisopropoxy methylene Althougha preference has been expressed for certain particular organicmaterials, it will be understood that this invention is applicable toall of those organic materials which form an acidic compound whentreated with an oxide or sulfide of phosphorus. These organic materialsinclude hydrocarbons such as olefins, diolefins, acetylenes,

aromatics, alkyl aromatics, alicyclics, petroleum fractions such aslubricating oil distillates, petrolatums, cracked cycle stocks orcondensation products of petroleum fractions, solvent extracts,petroleum fractions and the like.

The metal halides of this invention are preferably the chloridesalthough it will be understood that other halides such as bromide andiodidemay be employed if desired.

tentials include magnesium, aluminum, m nganese chroe rnium, iron,cadmium, and lead. Generally, the metals useful in the present inventionare those weakly basic metals from lead to magnesium, inclusive, in theelectromotive series of the metals.

The method of this invention is carried out by reacting the acidicphosphorus-containing organic compound with an aqueous acidic solutionof the metal halide at an elevated temperature for a period of timesufiicient to produce asubstantially dry metal salt of the acidicphosphorus-containing organic compound. It has been found that it isnecessary in order to obtain substantially complete conversion to themetal salt to add'a small amount of an acid which is preferably ahalogen acid such as HCl to the reaction mixture of the metal halide andthe acidic phosphorus-containing organic compound. .It is believed thatthe acid may serve, as a catalyst iniih'eji'eaction." Also the presenceof the acid probably prevents 4 the precipitation of undesirable metalsulfides and metal oxides in the reaction.

Since the reaction proceeds very slowly if the metal halide is added asa dry salt, it is preferable to utilize the metal halide in an aqueoussolution; In general, therefore, a preferred procedure in carrying outthis reaction comprises heating an oil solution of thephosphorussulfi-de reaction product to an elevated temperature betweenabout 220 F. and 300 F. and adding slowly to such heated solution anaqueous acidic solution of the metal halide. Water is driven off duringthe course of the reaction and when all of the aqueous solution has beenadded, the temperature of the resultant solution is raised to atemperature in the range'of 350 to 500 F. e

to assure completion of the reaction and elimination of substantiallyall of the Water.

An alternate procedure to the above-described method is one wherein amixture is initially formed comprising the aqueous solution of the metalhalide, the acidic phosphorus-containing organic material, and a smallamount of a halogen acid. This mixture is heated at an elevatedtemperature in the range of about 140 to 3O0f F, to commence thereaction and to remove water from the reaction mixture. Because of thepresence of water in the reaction mixture, care must be observed toprevent excessive foaming during the initial stages of the reaction inthis procedure. For this reason it is preferred to raise thetemperatures of the reaction mixture slowly in the range of about 140 to300 F. until a substantial portion of the water has'been driven off fromthe reaction mixture. Thereafter the reaction mixture may be furtherheated up to a temperature in the range of about 350 to 500 F. to assuresubstantial completion of the reaction between the metal halide and theacidic phosphorus-containing organic material. During the heating steps,halo'- gen acids originally present in the reaction mixture and thoseformed in the reaction as Well as the water originally present will beessentially removed by vaporization. A small amount of the halogen atomsderived from the metal halide or acid may remain in the final product.

The reaction time is generally not critical, the time required beingthat necessary for substantially completion of the reaction. A reactiontimein the range of about 1 to 10 hours will generally be sufiicient.The proportions of the ingredients are selected to give the desiredmetal salt of the acidic phosphorus-containing organic material. It isgenerally preferred to employ stoichiome'tric equivalents such that theacid groups are substantially completely converted to salt groups.However, where the acidic phosphorus-containing compounds are.polybasic, the proportion of metal halide employed can be such thatacid salts are obtained. When an excess of a polyvalent metal halide isemployed, mixed salts can be formed which contain both halogen and thephosphorus-containing group joined to the metal. In general, the acidicphosphorus-containing organic com pound is reacted with a suflicientamount of the metal halide to effect the neutralization of at leastabout 1% of the titratable acidity. If the reaction is permitted to besubstantially completed, the metal content of the resultant product willbe approximately equivalent to its concentration in the originalmixture. Although not essential, it is preferable for ease of reactionand handling of the finished product to use a diluentsuch as a petroleumlubricating oil base. in a preferred embodiment of this invention thereactants involved are phcsphosulfurized polyolefins and metalchlorides, in which reaction-the preferred acid catalyst is concentratedaqueousl-I'Cl. The;

amount of aqueous HCl utilized may be about 0.02 to 0.1 wt. percent,based on the total reaction mixture.

The following specific examples of the invention are presented to setforth the invention in greater detail, but it will be understood that itis not intended that these examples limit the invention in any way.

Example 1.Preparation of the zinc salt of PzSs-treated polybutene To 500grams of a PzSs-treated polybutene (made by reacting a polybutene havinga Staudinger average molecular weight of about 1200 with 10% by weightof P285 in a 4-liter beaker at 360 F.) was added a solution of 38 gramsof zinc chloride, 50 cc. of water and 15 drops of concentrated aqueoushydrochloric acid. The addition required 2 hours, and foaming occurredduring the addition. During the addition of the aqueous acidic zincchloride solution, the temperature of the contents of the beaker wasmaintained at a temperature of 400 to 440 F. After the aqueous acidiczinc chloride solution had been added, the temperature of the reactionmixture in the beaker was 440 F. and the temperature was then maintainedat 420 to 440 F. for a period of 2 hours. A clear liquid productresulted which was blended into a 50% concentrate with a solventextracted and dewaxed mineral lubricating oil base to form a concentratewhich had the following inspections by weight:

This concentrate was then utilized in preparing the followinglubricating oil composition:

Component: Weight percent 1. Concentrate containing zinc salt 10.0 2.Oil solution of polymerized isobutylene (M. W.=14,000) 9.0 3.Pass-treated a pinene 0.2 4. Mineral lubricating oil base 80.8

This lubricating oil composition had an SSU viscosity of 190.2 at 100 F.and 52.1 at 210 F. and a viscosity index of 149.

In other related experiments, it was found that the reaction between thezinc chloride and the Pass-treated polybutene proceeded very slowly ifthe zinc chloride was added as a dry salt rather than in an aqueoussolution. It was also found that if zinc oxide was used instead of zincchloride, apparently no reaction at all took place and the unreactedzinc oxide was left in the reaction mixture. When zinc oxide wasemployed, it was also found that the addition of an aqueous hydrochloricsolution appeared to initiate a reaction but it was also found thatsubstantial quantities of unreacted zinc oxide were present after aconsiderable period of heating.

Example 2.Preparatin of the tin salt of PzSs-tr'eated polybutene About500 grams of the PzSs-treated polybutene of Example 1 were blended withabout 333 grams of a mineral lubricating oil in a beaker. To this wasadded a solution of 44.6 grams of SuClz-ZHzO, 90 cc. of water, and 15drops of concentrated aqueous hydrochloric acid. The addition of theacidic aqueous tin chloride solution required about 2 hours, and foamingoccurred during the addition. During the step of adding this acidicaqueous tin chloride solution, the temperature of the reaction mixturein the beaker was maintained at a temperature of about 275 to 300 F.After the tin chloride solution had been added, the temperature of thereaction mixture was maintained at a temperature of about 300 F. for aperiod of /2 hour. A clear liquid product was obtained which had goodsolubility in oil.

Example 3.-Preparati0n of the cobalt salt of PzSs-treat d polybutene Thereaction was carried out with 1010 grams of a 60% solution by weight ofPass-treated polybutene in a mineral oil and an aqueous solutioncomprising 57.0 grams of CoClz-6H2O in cc. of water to which was added15 drops of concentrated hydrochloric acid. The oil solution ofPass-treated polybutene was heated to 260 F. and the aqueous cobaltchloride solution was then added over a period of 4.5 hours. During thisreaction period, the temperature was maintained between 235 and 300 F.When all of the aqueous solution had been added, the reaction mixturewas maintained for 3.5 hours at a temperature in the range of 240 to 400F. A nitrogen gas blanket was maintained over the reaction system duringthe entire reaction. The weight of the resultant product was 970 gramsand the product had the following elemental analysis:

Percent Cobalt 1.37 Phosphorus 1.58 Sulfur 0.88

75% by weight and to transport and store them in such form. In preparinga lubricating oil composition for use as a crankcase lubricant, theadditive concentration is merely blended with the lubricating oil basestock in the required amount.

The lubricating oil base stocks used in the compositions of thisinvention may be straight mineral lubricating oils or distillatesderived from paralfinic, naphthenic, asphaltic, or mixed base crudes,or, if desired, various blended oils may be employed as well asresiduals, particularly those from which asphaltic constituents havebeen carefully removed. The oils may be refined by conventional methodsusing acid, alkali and/or clay or other agents such as aluminumchloride, or they may be extracted oils produced, for example, bysolvent extraction with solvents of the type of phenol, sulfur dioxide,furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde, etc.Hydrogenated oils, white oils, or shale oil may be employed as well assynthetic oils, such as those prepared, for example, by thepolymerization of olefins or by the reaction of oxides of carbon withhydrogen or by the hydrogenation of coal or its products.

Other lubricating oil base stocks which may be employed includesynthetic lubricating oils having a viscosity of at least 30 SSU at 100P. such as esters of monobasic acids (e. g. ester of Ca Oxo alcohol withCa Oxo acid, ester of C13 Oxo alcohol with octanoic acid, etc.), estersof dibasic acids (e. g. di-2-ethyl-hexyl sebacate, di-nonyl adipate,etc.), esters of glycols (e. g. C13 Oxo acid diester of tetraethyleneglycol, etc.), complex esters (e. g. the complex ester formed byreacting one mole of sebacic acid with two moles of tetraethylene glycoland two moles of Z-ethyl-hexanoic acid, complex ester formed by reactingone mole of tetraethylene glycol with two moles of sebacic acid and twomoles of 2-ethyl hexanol, complex ester formed by reacting together onemole of azelaic acid, one mole of tetraethylene glycol, one mole of CaOxo alcohol, and one mole of Ca Oxo acid), esters of phosphoric acid (e.g. the ester formed by contacting three moles of the mono methyl etherof ethylene glycol with one mole of phosphorus oxychloride,

4 etc.), halocarbon oils (e. g. the polymer of chlorotri:

fluoroethylene containing twelve recurring units of chloro- I 7trifluoroethylene), alkyl silicates (e. g. methyl polysiloxanes, ethylpolysiloxanes,methyl-phenyl polysiloxanes, ethyl-phenyl polysiloxanes,etc), sulfite esters (e. g. ester formed by reacting one mole of sulfuroxychloride with two moles of the methyl ether of ethylene glycol,etc.), carbonates (e; g. the carbonate formed by reacting Cs OX alcoholwith ethyl carbonate to form a half ester and reacting this half esterwith tetraethylene glycol), mercaptals (e. g. the mercaptal formed byreacting 2- ethyl hexyl mercaptan with formaldehyde), formals (e. g. theformal formed by reacting C13 Oxo alcohol with formaldehyde), polyglycoltype synthetic oils (e. g. the compound formed by condensing butylalcohol with fourteen units of propylene oxide, etc.), or mixtures ofany of the above in any proportions.

Also, for special applications, animal, vegetable or fish oils or theirhydrogenated or voltolizecl products may be employed in admixture withthe synthetic or mineral oils. Also, mixtures of any of theabove-mentioned oils in any proportions may be employed.

For the best results the base stock chosen should normally be that oilwhich Without the new additive present gives the optimum performance inthe service contemplated. However, since one advantage of the additiveis that their use also makes feasible the employment of lesssatisfactory mineral oils or other oils, no strict rule can be laid downfor the choice of the base stock. Certain essentials must of course beobserved. The oil must possess the viscosity and volatilitycharacteristics known to be required for the service contemplated. Theoil must be a satisfactory solvent for the additive, although in somecases auxiliary solvent agents may be used. The

- lubricating oils, however they may have been produced, 'may varyconsiderably in viscosity and other properties depending upon theparticular use for which theyare desired, but they usually range fromabout 40 to 150 seconds Saybolt viscosity at 210 F. For the lubricatingof certain low and medium speed diesel engines the general practice hasoften been to use a lubricating oil base stock prepared from naphthenicor aromatic crudes and having a Saybolt viscosity of 210 F. of 45 to 90sec.

ends and a viscosity index of 0 to 50. However, in certain types ofdiesel engine and other gasoline engine service, oils of higherviscosity index are often preferred, for exanipla'up to 75 to 100, oreven higher, viscosity index.

In addition to the material to be added according to the presentinvention, other agents may also be used such as dyes, pour depressors,heat thickened fatty oils, sulfurized fatty oils, organo-metalliccompounds, metallic or other soaps, sludge dispersers, anti-oxidants,thickeners, viscosity index improvers, oiliness agents, resins, rubber,olefin polymers, voltolized fats, voltolized mineral oils, and/orvoltolized waxes and colloidal solids such as graphite or zinc oxide,etc. Solvents and-assisting agents, such as esters, ketones, alcohols,aldehydes, halogenated or nitrated compounds, and the like may also beemployed.

In addition to being employed in lubricants, the metal salts of thiinvention may be also used in motor fuels, hydraulic fluids, torqueconverter fluids, cutting oils, flushing oils, turbine oils ortransformer oils, industrial oils, process oils, gear lubricants,greases and generally as useful additives in oleaginous products. Themetal salts are also useful as flotation agents, fungicides,insecticides and the like. When utilized as fungicides or insecticides,the metal salts are preferably dispersed or dissolved in such materialsas water, organic solvents such as kerosene, light petroleum gas oils,etc., inert solids such as clay, and the like.

What is claimed is: V V a l. A method for preparing metallo organiccompounds which comprises reacting a phosphosulfurized hydrocarbon'inthe presence of a small amount of acid with a metal halide in aqueoussolution and in an amount suffi- 8 cient to form a metal salt of saidphosphosulfurized hydrocarbon, the reaction being carried out at atemperature and for a period of time sufficient to complete theresultant reaction and to form an essentially dry metalsalt, said metalbeing one which has an electrode potential in the1 electromotive seriesin the range of about 0 to 2.0 vo ts.

2. A method for'prcparing metallo-organic compounds which comprisesreacting a phosphosulfurized hydrocarbon in the presence of a smallamount of halogen caid with a metal halide in aqueous solution and in anamount sufiicient to form a metal salt of said phosphosulfurizedhydrocarbon, the reaction being carried out at a tempera- 3. A methodfor preparing metallo-organic compounds which comprises reacting aphosphosulfurized hydrocarbon in the presence of a small amount ofhalogen acid with a metal halide in aqueous solution and in an amountsufiicient to form a metal salt of said phosphosulfurized hydrocarbon,the reaction being carried out at a temperature in the range of about140 to 300 F. until a substantial portion of the Water is driven'off andthereafter at a temperature in the range of about 350 to 500 F. untilthe resultant reaction is substantially completed and essentially all ofthe water; present is removed, said metal being one which has anelectrode potential in the electromotive series in the rangerof about 0to 2.0 volts.

4. A method for preparing metallo-organic compounds which comprisesreacting a phosphosulfurized hydrocarbon in the presence of a smallamount of hydrochloric acid with a metal chloride in aqueous solutionand in an amount sufiicient to form a metal salt of saidphosphosulfurized hydrocarbon, the reaction being carried out at atemperature in the range of about 140 to 300 F. until a substantialportion of the Water is driven off and thereafter at a temperature inthe range of about 350 to 500 F. until the resultant reaction issubstantially completed and essentially all of the water present isremoved, said metal being selected from the group consisting of zinc,tin, nickel and cobalt.

5. Method according to claim 4 wherein said metal is zinc.

6. Method is tin.

7. Method is cobalt.

8. Method is nickel.

9. Method according to claim 4 wherein said phosphosulfurizedhydrocarbon is a PzSs-treated olefin polymer having a molecular weightin the range of about to 50,000.

10. A method for preparing metallo-organic compounds which comprisesreacting a Pass-treated polybutene in the presence of a small amount ofhydrochloric acid with a metal chloride in aqueous solution and in anamount sufficient to form a metal salt of said Pass-treated polybutene,the reaction being carried out at a temperature in the range of about to300 F. until a substantial portion of the water has been driven off andthereafter according to claim 4 wherein said metal according to claim 4wherein said metal according to claim 4 wherein said metal at atemperature in the range of about 350 to 500 F. until the resultantreaction is substantially completed and I enemas period of timesuflicient to complete the resultant reaction and to form an essentiallydry metal salt, said metal being one which has an electrode potential inthe electromotive series in the range of about 0 to 2.0 volts.

12. A chlorine-containing metallo-organic product obtained by reacting aphosphosulfurized hydrocarbon in the presence of a small amount ofhydrochloric acid with a metal chloride in aqueous solution and in anamount sufficient to form a metal salt of said phosphosulfurizedhydrocarbon, the reaction being carried out at a temperature in therange of about 140 to 300 F. until a substantial portion of the water isdriven 0E and thereafter at a temperature in the range of about 350 to500 F. until the resultant reaction is substantially completed andessentially all of the water present is removed, said metal beingselected from the group consisting of zinc, tin, nickel and cobalt.

13. As a new product, a polyvalent metal salt having at least onehalogen atom joined to said metal and also having at least one acidicgroup of a phosphosulfurized hydrocarbon joined to said metal, said salthaving been prepared by reacting a phosphosulfurized hydrocarbon in thepresence of a small amount of halogen acid with a metal halide inaqueous solution and in an amount sufficient to form said metal salt ofsaid phosphosulf urized hydrocarbon, the reaction being carried out at atemperature and for a period of time suificient to complete theresultant reaction and to form :an essentially dry metal salt, saidmetal being one which has an electrode potential in the electromotiveseries in the range of about 0 to 2.0 volts.

14. A lubricating oil composition comprising a major proportion of alubricating oil :and in the range of about 0.5 to 12% by weight of aproduct defined by claim 11.

15. A lubricating oil composition comprising a major proportion of amineral lubricating oil and in the range of about 0.5 to 12% by weightof a product defined by claim l2.

16. A concentrate consisting essentially of a lubricating oil and about20% to 75% by weight, based on the total concentrate, of a productdefined by claim 11;

References Cited in the file of this patent UNITED STATES PATENTS2,316,091 White Apr. 6, 1943 2,383,043 Farrington Aug. 14, 19452,476,037 Giammaria July 12, 1949 2,689,827 Hook Sept. 21, 1954

1. A METHOD FOR PREPARING METALLO-ORGANIC COMPOUNDS WHICH COMPRISES REACTING A PHOSPHOSULFURIZED HYDROCARBON IN THE PRESENCE OF A SMALL AMOUNT OF ACID WITH A METAL HALIDE IN AQUEOUS SOLUTION AND IN AN AMOUNT SUFFICIENT TO FORM A METAL SALT OF SAID PHOSPHOSULFURIZED HYDROCARBON, THE REACTION BEING CARRIED OUT AT A TEMPERATURE AND FOR A PERIOD OF TIME SUFFICIENT TO COMPLETE THE RESULTANT REACTION ANF TO FORM AN ESSENTIALLY DRY METAL SALT, SAID METAL BEING ONE WHICH HAS AN ELECTRODE POTENTIAL IN THE ELECTROMOTIVE SERIES IN THE RANGE OF ABOUT 0 TO 2.0 VOLTS. 